1. FIELD OF THE INVENTION
The invention relates to new 4-thiomethylpyrazole compounds, related compounds, compositions containing them, processes for their preparation, and their use for the control of arthropod pests (especially insects) and nematodes.
2. DESCRIPTION OF THE RELATED ART
Pesticidal N-arylpyrazoles are described in the art, for example, in EP 0234119, EP 0511845, EP 0352944 and EP 0295117.
The present invention provides a compound of formula (I): 
wherein:
Q is a group (A1) or (A2): 
W is N or CR6;
xe2x80x94X1xe2x80x94X2xe2x80x94X3xe2x80x94 is xe2x80x94CF2CF2Oxe2x80x94, xe2x80x94CF2OCF2xe2x80x94 or xe2x80x94OCF2Oxe2x80x94;
R1 is alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkyl, cycloalkylalkyl or xe2x80x94(CH2)mR7; or is naphthyl optionally substituted by alkyl, haloalkyl, halogen, NO2, alkoxy, haloalkoxy or R8S(O)p;
R2 is hydrogen, halogen or optionally substituted amino;
R3 and R6 are each independently hydrogen or halogen;
R4 is hydrogen or haloalkyl;
R5 is hydrogen, halogen, haloalkyl, haloalkoxy, xe2x80x94S(O)pCF3 or SF5;
R7 is phenyl or a five to seven membered heteroaromatic ring having from one to four heteroatoms which are the same or different selected from nitrogen, oxygen and sulfur, which ring is optionally substituted by R9;
R8 is alkyl or haloalkyl;
R9 is alkyl, haloalkyl, halogen, CN, NO2, R10O, R8S(O)p, C(O)R8, C(O)OR10 or NR10R11; or when R7 is phenyl two adjacent R9 groups together form a xe2x80x94CF2OCF2xe2x80x94 or xe2x80x94OCF2Oxe2x80x94 group;
R10 and R11 are each independently hydrogen, alkyl or haloalkyl; and
m, n and p each independently have the value zero, one or two;
or an agriculturally acceptable salt thereof.
The compounds of formula (I) and the agriculturally acceptable salts thereof as defined above possess valuable pesticidal properties. The compounds of the invention show improved pesticidal activity in comparison with known compounds.
The invention also encompasses any stereoisomer, enantiomer or geometric isomer, or mixture thereof, of the compounds of formula (I).
By the term xe2x80x9cagriculturally acceptable saltsxe2x80x9d is meant salts the cations or anions of which are known and accepted in the art for the formation of salts for agricultural or horticultural use. Suitable salts with bases include alkali metal (e.g. sodium and potassium), alkaline earth metals (e.g. calcium and magnesium), ammonium and amine (e.g. diethanolamine, triethanolamine, octylamine, morpholine and dioctylmethylamine) salts. Suitable acid addition salts, e.g. formed by compounds of formula (I) containing an amino group, include salts with inorganic acids, for example hydrochlorides, sulfates, phosphates and nitrates and salts with organic acids for example acetic acid.
Unless otherwise specified, alkyl, acyl and alkoxy groups (or portions thereof) are straight- or branched- chain and have from one to ten (preferably one to six) carbon atoms.
Cycloalkyl groups have from three to six carbon atoms in the ring and are optionally substituted by alkyl or halogen.
Alkenyl and alkynyl groups or portions thereof are straight- or branched-chain and have from two to eight (preferably two to four) carbon atoms.
The term xe2x80x9chaloxe2x80x9d before the name of a radical means that this radical is partially or completely halogenated, that is to say, substituted by F, Cl, Br, or I, in any combination, preferably by F or Cl. The term xe2x80x9chalogenxe2x80x9d means F, Cl, Br or I.
A preferred embodiment of the invention comprises a compound of formula (I) wherein Q, R1 and n are as defined above and R2 is xe2x80x94NR12R13 or xe2x80x94Nxe2x95x90C(R10)(R14), wherein:
R12 and R13 are independently selected from hydrogen, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, xe2x80x94C(O)R15 and C(O)OR15; or R12 and R13 are joined together to form a divalent radical having 4 to 6 atoms in the chain, this divalent radical being alkylene, alkyleneoxyalkylene or alkyleneaminoalkylene (preferably forming a morpholine, pyrrolidine, piperidine or piperazine ring);
R14 is alkoxy or haloalkoxy; or is phenyl optionally substituted by alkyl, haloalkyl, hydroxy, halogen, alkoxy, xe2x80x94S(O)pR8 or CN;
R15 is alkenyl, haloalkenyl, alkynyl or haloalkynyl; or is alkyl optionally substituted by halogen, alkoxy, C(O)R8, C(O)OR10, CN, xe2x80x94S(O)pR8, or CONR10R11.
Preferred compounds of formula (I) are those in which R1 is alkyl, haloalkyl, cycloalkyl or naphthyl; or phenyl optionally substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy or NO2; or pyridyl optionally substituted by halogen or haloalkyl; or xe2x80x94CH2R7 wherein R7 is phenyl optionally substituted by halogen, alkyl or alkoxy; or xe2x80x94CH2CH2R7 wherein R7 is phenyl.
Preferred compounds of formula (I) are those in which Q is a group (A1) wherein:
W is N or CR6; R3 and R6 are each independently hydrogen or halogen; R4 is hydrogen; and R5 is halogen, CF3, OCF3 or SF5; or wherein:
W is N or CR6; R3 and R6 are each independently hydrogen or halogen; R4 is CF3; and R5 is hydrogen.
More preferred compounds of formula (I) are those in which Q is a group (A1) wherein:
W is CR6; R3 is hydrogen or halogen; R6 is halogen; R4 is hydrogen; and R5 is halogen, CF3 or OCF3; or wherein:
W is CR6; R3 is hydrogen; R6 is halogen; R4 is CF3; and R5 is hydrogen.
Preferred compounds of formula (I) are those in which R2 is xe2x80x94NR12R13 or xe2x80x94Nxe2x95x90C(R10)(R14).
More preferred compounds are those in which R2 is xe2x80x94NR12R13 or xe2x80x94N=C(R10)(R14), wherein R12 is hydrogen, alkyl or xe2x80x94C(O)R15; R13 is hydrogen or alkyl; R10 is hydrogen; R14 is alkoxy; and R15 is alkyl.
Yet more preferred compounds are those in which R2 is xe2x80x94NHR13 or xe2x80x94Nxe2x95x90CH(R14); wherein R13 is hydrogen or alkyl; and R14 is alkoxy.
Compounds in which R2 is amino are most preferred.
Compounds in which n is 1 or 2 are also preferred.
A preferred class of compounds of formula (I) are those in which:
R1 is alkyl, haloalkyl, cycloalkyl or naphthyl; or phenyl optionally substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy or NO2; or pyridyl optionally substituted by halogen or haloalkyl; or xe2x80x94CH2R7 wherein R7 is phenyl optionally substituted by halogen, alkyl or alkoxy; or xe2x80x94CH2CH2R7 wherein R7 is phenyl;
Q is a group (A1) wherein:
W is N or CR6; R3 and R6 are each independently hydrogen or halogen; R4 is hydrogen; and R5 is halogen, CF3, OCF3 or SF5; or wherein:
W is N or CR6; R3 and R6 are each independently hydrogen or halogen; R4 is CF3; and R5 is hydrogen; and
R2 is xe2x80x94NR12R13 or xe2x80x94Nxe2x95x90C(R10)(R14); wherein R12 is hydrogen, alkyl or xe2x80x94C(O)R15; R13 is hydrogen or alkyl; R10 is hydrogen; R14 is alkoxy; and R15 is alkyl.
A further preferred class of compounds of formula (I) are those in which:
R1 is alkyl, haloalkyl, cycloalkyl or naphthyl; or phenyl optionally substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy or NO2; or pyridyl optionally substituted by halogen or haloalkyl; or xe2x80x94CH2R7 wherein R7 is phenyl optionally substituted by halogen, alkyl or alkoxy; or xe2x80x94CH2CH2R7 wherein R7 is phenyl;
Q is a group (A1) wherein:
W is N or CR6; R3 and R6 are each independently hydrogen or halogen; R4 is hydrogen; and R5 is halogen, CF3, OCF3 or SF5; or wherein:
W is N or CR6; R3 and R6 are each independently hydrogen or halogen; R4 is CF3; and R5 is hydrogen;
R2 is xe2x80x94NR12R13 or xe2x80x94Nxe2x95x90C(R10)(R14); wherein R12 is hydrogen, alkyl or xe2x80x94C(O)R15; R13 is hydrogen or alkyl; R10 is hydrogen; R14 is alkoxy; and R15 is alkyl; and
n is 1 or 2.
A further preferred class of compounds of formula (I) are those in which:
R1 is alkyl, haloalkyl, cycloalkyl or naphthyl; or phenyl optionally substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy or NO2; or pyridyl optionally substituted by halogen or haloalkyl; or xe2x80x94CH2R7 wherein R7 is phenyl optionally substituted by halogen, alkyl or alkoxy; or xe2x80x94CH2CH2R7 wherein R7 is phenyl;
Q is a group (A1) wherein:
W is CR6; R3 is hydrogen or halogen; R6 is halogen; R4 is hydrogen; and R5 is halogen, CF3 or OCF3; or wherein:
W is CR6; R3 is hydrogen; R6 is halogen; R4 is CF3; and R5 is hydrogen; and R2 is xe2x80x94NHR13 or xe2x80x94Nxe2x95x90CH(R14); wherein R13 is hydrogen or alkyl; and R14 is alkoxy.
Methods or Processes of Synthesis
The compounds of general formula (I) can be prepared by the application or adaptation of known methods (i.e. methods heretofore used or described in the chemical literature).
Compounds of general formula (I) wherein R1, R2 and Q are defined above and n is zero may be prepared by the reaction of a compound of formula (II): 
wherein R2 and Q are defined above, with a thiol of formula (III):
R1SHxe2x80x83xe2x80x83(III)
wherein R1 is as defined above, in the presence of a Lewis acid, preferably boron trifluoride etherate, to give a hemithioacetal intermediate of formula (IV): 
which is not generally isolated, and is treated in situ with a reducing agent generally a hydrosilane derivative (i.e. a silane which contains one or more hydrogen atoms), preferably a trialkylsilane such as triethylsilane. The reaction is generally performed in a chlorinated solvent such as 1,2-dichloroethane, at a temperature of from 0xc2x0 to 60xc2x0 C.
Compounds of general formula (I) wherein R1, R2 and Q are defined above, and n is 1 or 2 may be prepared by oxidizing a corresponding compound in which n is 0 or 1. The oxidation is generally performed using a peracid such as 3-chloroperbenzoic acid in a solvent such as dichloromethane, or with hydrogen peroxide generally in the presence of trifluoroacetic acid, at a temperature of from 0xc2x0 C. to the reflux temperature of the solvent.
These processes are also an object of the invention.
Compounds of general formula (I) wherein R1, Q and n are as defined above, and R2 is as defined above with the exclusion of amino, may be prepared from the corresponding compounds in which R2 is amino by the application of known methods for example as described in European Patent Publication Numbers 0234119, 511845, 352944 and 295117.
If desired, a compound of formula (I) produced by any of the above process embodiments may be converted into an agriculturally acceptable salt thereof.
Intermediates of formula (II) wherein R2 is amino are known or may be prepared by known methods, for example by the Vilsmeier formylation of compounds of formula (V): 
using phosphoryl chloride and N,N-dimethylformamide at a temperature of from 0xc2x0 to 50xc2x0 C. to give a compound of formula (VI): 
which is hydrolyzed, generally under acidic conditions, for example using hydrochloric acid, in a solvent such as tetrahydrofuran at a temperature of from 0xc2x0 to 100xc2x0 C.
Intermediates of formulas (III) and (V) are known or may be prepared by known methods.
The invention is illustrated by the following non-limiting examples, and in the tables it will be understood that xe2x80x98Mexe2x80x99 means methyl, xe2x80x98Etxe2x80x99 means ethyl, xe2x80x98i-Prxe2x80x99 means isopropyl, xe2x80x98t-Buxe2x80x99 means tert butyl, and xe2x80x98Phxe2x80x99 means phenyl.